Azo dyes



Patented Sept. 12, 1944 AZO DYES Swanie S. Rossander,Wilmington, Deli, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing.

4'Olaims.

'I'hisinvention. relates to azo dyestufisand to intermediates from which the dyestuffs may be made by simple processes.

It is an object of theinvention to prepare new azo dyestuffs which have colors similar to dyestufis known to the priorart but, which are possessed of improved properties, particularly washing fastness and substantivity. In order to: accomplish the objects I have been obliged to make new products which are direct dyes and subsequently diazotize and couple these products on the fiber'with developing agents to form the com pleted. dye. Inasmuch as both intermediateprodnets" and completed dyes are new and useful I claim. them both.

Broadly speakingtheobjects of the invention are accomplished bycoupling products of the type OH with a diazotized arylamine to formthe new in-.

termediate products' which can be used to form the final color by applying to cellulose. or regenerated cellulose from an aqueous bath, diazotizingon the fiber, and coupling to a component, such as beta naphthol.

An alternative method of producing the inter-, mediate products is to condense an amino-azo compound with a dim'tro-aroyl-halide, reduce it, condense the reduction product with nitro-aroylhalide, and again reduce under conditions such ApplicationFebruary 23, 1938, Serial No. 191,973

Example -I Add 27.9 parts of aniline to 1000 parts of water. Add 29.2 parts of hydrochloric acid. 0001 to C. by adding 1500 parts of ice. Add 20.7 parts of sodium nitrite as 30% solution as rapidly as absorbed, maintaining 0 C. temperature,

Con-go acidity and a slight excess nitrite for twen-' ty-five minutes.

Slurry 198 parts of di(para-amino-benzoyl)- 3:5-diamino-benzoyl J -acid, sometimes referred to herein as (di-PAB) -3:5-DAB-J-acidwith 9500 parts of water. Add 40'parts of 29% ammom'a solution and stir one-half hour at 20 C. Add '70 parts of Z-Normal sodium hydroxide to give complete solution. Add parts of sodium bicarbonate and, 400 parts of 2-Normal soda-ash solution. Cool to 0 C. with ice. Slowly add the diazobenzene solution to the agitated solution. Stir the mixture allowing it to come to room temperature during three or morehours. Maintain a definite alkalinity to Brilliant Yellow paper and an excess of (di-PAB) 3:5-DAB-J- acid. Heat to 70 C. Add sodium chloride (about 10%) until a test portion on filter paper shows a reasonable clean rim. Filter and dry.

The dried product is an orange-red powder,

dyeing cotton shades of orange. When these dyeings are diazoti'zed and developed with betanaphthol, shades of red-orange are obtained.

The above dye has the following structural formula:

V I Example II (Alternative method) Add 47 parts of aniline to 200 parts of ice and then add 45.6 parts of hydrochloric acid. Diazotized at C. with 34.5 parts of sodium nitrite adding moreice'as necessary. Maintain a definite acidity to Congo red paper and a slight excess of nitrite for minutes.

Slurry 120 parts of J-acid with 2000 parts of water and dissolve with 53 parts of soda ash leaving the solution slightly alkaline to Brilliant Yellow paper. Add 132.5 parts of soda ash and ice 'the solution to 0 C.

Run th diazobenzene solution slowly into the alkaline J-acid solution with good agitation.

Keep strongly alkaline to Brilliant Yellow paper and maintain an excess of J -acid. Stir at least 3 hours Heat to 65 C. and add salt. Stir 2 hours at 65 C. and filter.

dissolved in carbon tetrachloride in small portions.

Approximately 75 parts. of soda ash are required. Filter off the product.

Slurry the press-cake with 4000 parts of water and add 10 parts of soda ash. Heat to 60-65 C.

V and add 165 parts of sodium disulfide slowly as required to maintain a moderate excessias shown by the nitroprusside test. One hour after all the sodium disulfide has been added, add 10 salt and filter.

. Normal hydrochloric acid, followed immediately by 160 parts of 2-Normal sodium nitrite. Maintain Congo acidity and anexcess of nitrite for I 20' minutes.

Dissolve 66 parts of di- (meta-amino-benzoyl) 3 5-diamino-benzoyl J -acid in 3000 parts of water and just enough ammoniumhydroxide to dissolve. Add 30 partsbf sodium bicarbonate and 160 parts of 2-Normal soda ash solution. Cool to 10 C. Slowly add the diazo of amino-azobenzene-sodium sulfonate with good agitation. Stir 3 hours allowing the temperature to rise 20 .0. Slowly heat to 70 0. Add sodium chloride and isolate the product in the manner described 7 in Example I.

The dried productis of reddish color. It dyes cotton shades of red. Developed dyeings (with beta-naphthol) are also red in color.

The structural formula of the product follows:

0 H I] N-C 0 r I H II C NH: lTlH:

HOzS

' Example IV line to Brilliant Yellow paper. Cool to 5 C. Add 150 parts of IU-Normal-hydrochloric acid solution, followed by the addition of 250 parts of 2-,

. Normal sodium nitrite solution as rapidly as ab- Take up theVpress-cake'in 2000 parts ofwater' and heat to 65 0. mm stirring. Keep alkaline toBrilliant Yello paper with soda ash while adding '204 parts of .p-nitro-benzoyl chloride dissolved in carbon tetrachloride in small portions.

Approximately W 120 parts of soda ash are required. Filter off the product, which should out of solution. x o Slurrythe press-cake with 2000 parts of. water and heat to'65-70" C. Add 10 parts of soda ash.

Add 165 parts of sodium disulfide slowly main- 'taining atall times'a medium excess: as shown by the'nitro-prusside test. One hour after the last addition of sodium disulfide filter off the dye. Dry in an oven at -90 C.

The dried product is an orange-red powder, 7

dyeing cotton shades an, orange. When these dyeings are diazotized and developed with beta naphthol, shades of. red-orange are obtained.

ENG-CONE.

SOzNa The dye is represented by the same structural formula as Example I.

Example III Slurry 34 parts of 4-amino-azo-benzene-4 sodium sulfonate with parts of water- Warm sorbed. Keep a slight excess of nitrite for 30 minutes at 0-5 C.

3z5-diamino-benzoyl J-acid with'10,000 parts of waterat 25 C. Cautiously add 60 parts of 29% ammonia solution and stir 20 minutes. Add ,70 parts of 2-Normal sodium hydroxide to give complete solution. Add parts ofsodium bicarbohate and 1000 parts of 2-Normal soda ash solu-.

tion. Cool to 0 C. Slowly add the tetrazo of benzidine 3:3'-disulfonic acid tothe solution of I V dyeing,'which becomes brown after development with beta-naphthol.

The formula for thedye'is:

NHCO: NH1

NaOaS NH0 0 SOsNa I H The following table isa partial and representative list of the new colors. list the first column refers to the diazo component, the second to the couplingcomponent; the third to the color produced directly on cellulose from an aqueous bath containing" the intermediateand the to solution. Cool to 60 C. Add 30 parts of 10- 75 fourth the color produced'on cellulose by diazotiz- Add caustic soda Slurry 312 parts of di-(para-amino-benzoylla Maintain strong alkalinity. 0n Brilliant iiIHooONH. A

ingi the. cellulose and impregnating with the intermediate and developing with beta-naphthol. In this table the expression PAB means paraamino-benzoyl, DAiBmeans diaminoebenzoyl, and MAB means meta-amino-benzoyl.

The: developing agents used'for" coupling. to the diazotized products of the dyes of thisinvention are preferably beta naphthol' and. 1-phenyl-3-- methyl-5-py razolone, but acetoacetanilide, meta- 5 tolyl'ene-diamine are also" useful.

Sh ade of dyeing Coupling component Direct Developed Diazotized component Aniline 'o-Anisidine.... 2: 5-din1ethoxy-aniline Anthranilic acid 4-ch1oro-anilinefi-sulfonic-acid. Beta-naphthyl amine 'l-naphthylaminei sulfonic-aold 2-naphthy1amine-6:S-disulfonic acid H-acid 4-aniino-azobenzene-4-s111fonic-acid 4-amino-3 2 3 -dimethyl-azobenzene-4 -su1fon1c-ac1d. 50% o-anisidine, 50% beta-naphthyl-amine Aniline p-Phenetidine... p-Amino-benzoic-acld. p-Zylidine Beta-naphthylamine 4-an1jno-azobenzene-4-sulfonic acid.

Amllne 26.. 2-naphthylamineefizs-disulfo id metatoluidine (condensed with 'para-nitro-benzoyl-chloride and nitro reduced to amino).

27..-.. 2-naphthylcmine-6:8disu1fonic-acid meta-toluidine meta toluidine.

28.-... Snlfanilic acid meta toluidine 29..... 4-amino-azo-benzcne-4-sodium-sulfonate di(PAB)- 3:5-DAB-l-acid :3

30... l-amino-benzene-S-sulfonic acid 2:5-dimethoxy-aniline di(PAB)-3-DAB-J-acid Tetrazo component r Benzidine-3:3-disulfonic acid 4:4-diamino-diphenyl-methane-3 :3-dicarboxylic acid. 4 :4-diamino-diphenyl-urea-3 3-disulfonic acid 3:3-diamino-azoxy-benzene-monorsulfonic acid Para-amino-benzoyl-meta-phenylene-diamine The aroyl group, Aryl--Co, can also be Aryl S02 in the formulae of this invention. For instance, a coupling ArylCONH'-Aryl can also be ArylSO2NHAryl by using the-'sulfonic acid pling component so that the completed compound, vwhen coupled on the fiber with beta naphthol, will not be very soluble.

All of the nucleiof the completed compounds of all types may have substituents suchas hydroxy, amino, nitro, alkyl, alkoxy, acetylamino; halogen, carboxylic and sulfonic acid.

Di(PAB)-3:5-DAB-J-acid... .-...do R d .-...do .L

[Di(PAB)-3:5-DAB-J-acid] 1 Red-orange.

S-D'A G mrna acid.... :5-DAB-J-acid Di(M'AB)-3:5-D AB-J-acid Di(PAB)-3:5 DAB-J-acid5 (J-acidh Reddish brown. Orange.

. Brown.

[Di(PAB)'-3 5-.DAl3-J' acid] '2 The following examples illustrate; the production of the completed compounds onthe fiberJ Example XXXVI for condensation in place of the carboxylic acid. 45 I The arylamine used as the azo component may Five parts of cotton piece goods is dyed in the be of the benzene, napht ale e, anthracene, diusual manner, known to those, skilled in the art, phe y d p enyl et a e o stilbene series. It with two hundredths parts of aniline Di- (par s:

. u of u s hav an amino group capable of amino benzoyh 3 51.- diamino-benzoyl-J-acid. diazfitizationsohlbilizlng groups, h as bo The. dyed fabric isrinsed in cold. Water and put ionic and carboxylic acid, are preferred as sub- '11,1200lmrtswofrWateratv 20p C. Add'threEteriths re a to the number present in the cow sulfuric; acid. Stir 15 minutes. Rinse with cold g i 55 water. Dissolve one-tenth part of beta naphthol in 200 parts of Water and one-twentieth part of caustic soda. Stir the solution rap-idlywhile adding the above rinsed piece goods. Stir for 15 minutes. Rinse in cold water and dry, The dyeing is a bright orange shade. The probable formula of the dye on the fiber is:

I eeQ- W V mNGooNH 7 methods further illustrate the colors ;which can .OH SOaNa 3. A compound represented by the formula:

V 9 -C -NHCC I I NnooQ-mn Naois I SOaNa OH 4. The method which comprises diazotizinga compound represented by the formula:

be produced upon the fiber by the process of this Ary1( NH2).n lnVel'ltlOIl. 7 7 p I I in which aryl 1s a single nucleus from the class Ex. v V Diazo component Coupling component Shade on cellulose 37.....- 2-naphthylamine-6:8-disulfonic acid meta-toluidine (condensed with Beta naphthol Orange.

7 %iieinitro laenzoyl-chloride and reduced to amine) d1-(MAB)-3:5- g

' -ac1 V e Aniline di'-(PAB)-3:5-DAB-J-acid .l l-phenyl-8-methyl-5-pyrazolone. Yellow orange.

do Acetoacet-anilide; Do. I 4 do Meta-tolylene-diamine Brown.

H-acid cresidine di-(MAB)-3:5-DAB-J-acid 1-pheny1-3-methyl-5-pyrazclone Green. 4-amino-azobenzeneA-sulfonic acid di-(PAB)-3:5-DAB-.l-ac1d. Beta naphthol Red. 7 4'-aminO-3:3-dimethy1-az0benzene-4-su]Ionic acid d1-(PAB)- do D0. j

DAB-J-acid. 4-ami.no:azobenzenel-sulfonic acid di-(MAB )-3: -DAB-J-ac1d d0 D0- The colors produced by this invention are of outstanding fastness towashing, of exceptional aflinity for cellulose (by which term is meant the in which n and n are the same member of a class of digits consisting of 1 and 2, aryl' is a single aromatic nucleus from the class consisting of .diphenyl, and a'zobenzene, and each said nucleus has at least one member of the class consisting of hydrogen, halogen, alkyl, alkoxy, amino, nitro, acetyl-amino, carboxyl, and sulfonic acid. 2. A compound represented by the formula? consisting of diphenyl, and .azobenzene, and n is a digit from the class consisting of 1 or 2,' and coupling it to n-molsof a component having the formula:

V NH: Nnoog NHOC w I /A x OH V. each nucleus of either compound having at least one member from the'class consisting of hydrogen, halogen, alkyl, alkoxy,amino-n itro, acetylamino, carboxy, and sulfonic acid. 1

- CERTIFICATE OF CORRECTION. Patent No. 2,557,977. r September 12, 19th.

SWANIE s. RO'SSANDER.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, in the formula at the bottom of the page, for -"N-N" both occurrences, read --N=N; and that the said Letters Patent shouldbe read withthis correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 7th day of November, A. D. 1914A.

Leslie Frazer (Seal) Acting Commissioner of Patents. 

